CN110204130B - Wastewater treatment device and method containing heavy metal and radioactive uranium elements - Google Patents
Wastewater treatment device and method containing heavy metal and radioactive uranium elements Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention relates to the technical field of environmental protection, in particular to a device and a method for treating wastewater containing heavy metal and radioactive uranium elements, which comprises a resin adsorption unit, an diffusion and permeation membrane separation unit, an acid concentration and evaporation unit, an alkaline reaction precipitation and evaporation crystallization unit, a tail gas absorption treatment unit and other process flows, wherein the removal and separation can be thoroughly realized by treating acidic water containing radiation protection, salt and heavy metal, the safety and environmental protection requirements can be met, and the removal efficiency of the uranium elements with the properties of recycling resources and radiation protection is high; the safety of personnel is ensured by realizing full automation of the resin adsorption automatic charging and discharging processes; the nitric acid is concentrated, evaporated, recycled and reused, so that resources are saved; carrying out liquid-solid packaging treatment on the heavy metal by carrying out basic reaction, precipitation and evaporation on crystallized salt; the tail gas after evaporative crystallization is absorbed and then discharged to ensure the requirement of tail gas emission; has the advantages of simple process, safety, environmental protection and resource saving.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a device and a method for treating wastewater containing heavy metal and radioactive uranium elements.
Background
Uranium-bearing radioactive acidic water is a type of radioactive wastewater from a wide variety of sources, such as mining and preparation of uranium ores, uranium refining and nuclear fuel manufacturing wastewater, reactor operation wastewater, reactor fuel reprocessing wastewater, wastewater from radioisotope production, and wastewater from factories and research departments in which radioisotopes are used. The in-situ leaching uranium mining is to inject leaching solution prepared according to a certain formula into a natural ore-containing aquifer through liquid injection and drilling, to selectively oxidize and dissolve uranium under the action of hydraulic gradient along the ore bed, to form uranium-containing solution, to be lifted to the ground surface through liquid extraction and drilling, and to obtain the required uranium concentrate product through hydrometallurgy. Because the acid leaching process is mostly adopted in the in-situ leaching uranium mining mine in China, SO in underground water after the mining area is retired4 —2、NO3 —、U(VI)、H+And many components such as heavy metal ions are seriously out of the limits.If the pollutants are not treated in time, the pollutants threaten the downstream underground water resources through the infiltration and migration, and have great influence on the industrial and agricultural production and the drinking water safety of human beings.
Currently, the adsorption method, the evaporation concentration method and the extraction method are commonly adopted. The adsorption method is based on an adsorbent, has high selectivity to radioactive elements, is high in cost, and cannot treat acid salts. The evaporation concentration method simultaneously concentrates metal impurities and salt, and partial waste liquid is mixed with radioactivity and is pretreated, so that the treatment cost is high and the effect is poor. The extraction method is to add a solvent which is insoluble in water to dissolve radioactive pollutants in the waste acid water in the solvent, then separate the solvent from the waste water, and the waste water containing the pollutants after separation has higher radioactivity, and the salt can not be completely removed and separated from other metal ions.
Aiming at the problems, the device and the method for treating the wastewater containing the heavy metal and the radioactive uranium element can realize the removal of the radiation-proof element; the heavy metal and salt are removed and collected, so that the resource is saved, clean acid can be recovered for reuse, the requirements of safety and environmental protection on discharge are met, the water environment is protected, and the method has a good application prospect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a device and a method for treating wastewater containing heavy metal and radioactive uranium elements, which have the advantages of simple process, safety, environmental protection and resource saving; the innovation points are as follows: the adopted process for removing radioactive elements and heavy metals Fe, Ni and Cr adopts a special resin adsorption process, a diffusion and permeation chromatography membrane for separating heavy metals and an acid evaporation and concentration recycling process, and completely realizes safe, environment-friendly and integrated packaging system treatment equipment.
The technical scheme adopted by the invention for solving the technical problems is as follows: a waste water treatment device and method containing heavy metal and radioactive uranium element, including resin adsorption unit, diffusion and permeation membrane separation unit, acid concentration and evaporation unit, alkali reaction precipitation and evaporation crystallization unit, tail gas absorption and treatment unit and other process flows, mainly including the following steps: 1) pumping wastewater containing acid, salt, heavy metal and radioactive uranium element into the resin adsorption unit through a pump for adsorption treatment, and pumping radioactive wastewater desorbed by resin into a calcination treatment process through a pump; 2) discharging the clear liquid adsorbed by the resin to the dialysis membrane separation unit, and separating acid water and heavy metals; 3) clean acid is discharged to the acid concentration evaporation unit for concentration process treatment after the diffusion chromatography membrane separation; 4) heavy metal residual liquid separated by the diffusion and permeation separation membrane enters the basic reaction precipitation evaporation crystallization unit for treatment; 5) carrying out solid waste treatment on the precipitated salt through evaporative crystallization packaging; 6) condensing and recovering water evaporated by acid concentration to be used as membrane separation pure water for supplementing water; 7) and the tail gas after the evaporation crystallization is washed and demisted by the tail gas absorption unit for emission.
The invention is further configured to: the features of the utility meter line include: 1) the pipelines, valves and other accessories in contact with the liquid in the reactor are made of corrosion-resistant materials; 2) all parts are required to be fully welded, and flaw detection treatment is carried out on the welding parts; 3) and the surface of the equipment (such as a tank body, an auxiliary system and the like) is required to be polished (surface roughness after polishing: and (3) outside: ra2.4, inner ra0.8); 4) the pressure transmitter, the thermocouple, the digital display meter, the motor, the instrument and the like related to the equipment are made of corrosion-resistant materials; 5) remote control is adopted, and the interlocking alarm function is that the equipment performs the related interlocking alarm function in the process.
The invention is further configured to: all the equipment of the process flows such as the resin adsorption unit, the diffusion dialysis membrane separation unit, the acid concentration evaporation unit, the basic reaction precipitation evaporation crystallization unit, the tail gas absorption treatment unit and the like are installed by adopting an integrated device, are intensively installed in a glove box, and are operated and overhauled through a glove hole or in a long distance.
The invention is further configured to: the resin adsorption unit comprises a radioactive wastewater tank, a wastewater feeding pump, a resin adsorption column and a security filter, wherein the radioactive wastewater tank is connected with the wastewater feeding pump through a pipeline, wastewater is injected into the resin adsorption column, the resin adsorption column comprises a first adsorption column and a second adsorption column, the first adsorption column is used for adsorption, the second adsorption column is used for resolution, the first adsorption column is connected with the second adsorption column in parallel, the resin adsorption column is connected with the security filter through a pipeline, residual liquid of the resin adsorption column is discharged to a calcination position for treatment, and clear liquid after adsorption is discharged to the security filter for secondary filtration.
The invention is further configured to: the dialysis membrane separation unit comprises a diffusion and dialysis membrane separator, a heavy metal collecting tank, a condensate recovery pump and a tail gas washing pump, clear liquid filtered by the cartridge filter enters the diffusion and dialysis membrane separator, one side of the diffusion and dialysis membrane separator is connected with pure water through a pipeline, one part of the clear liquid is connected with the condensate recovery pump and the tail gas washing pump through pipelines, and residual liquid discharged from the lower part of the diffusion and dialysis membrane separator is connected with the heavy metal collecting tank through a pipeline.
The invention is further configured to: the acid concentration evaporation unit comprises an evaporation concentration tower, a condenser, a condensate tank and an acid recovery pump, clear liquid discharged by the diffusion and permeation separation membrane separator is connected with the evaporation concentration tower through a pipeline, and the evaporation concentration tower is connected with the condenser through a pipeline for heating evaporation and concentration of acid through steam; the water condensed by the condenser is connected with the condensed liquid tank by a pipeline; and acid concentrated by the evaporation concentration tower is pumped into a recovery system through the acid recovery pump, and water condensed by the condensate tank is pumped into the dialysis membrane separator through the condensate recovery pump to be used as water supplement.
The invention is further configured to: heavy metal collection tank passes through the pipeline and is connected with heavy metal raffinate charge-in pump, sets up lye tank and alkali lye charge-in pump for the pipe connection, heavy metal raffinate charge-in pump raffinate with alkali lye charge-in pump alkali lye gets into basic reactor together through the pipeline, the precipitate of basic reactor reaction gets into the filter and filters the sediment, the filterable precipitate of filter gets into liquid and changes solid evaporimeter and evaporate the crystallization salt, liquid changes solid evaporimeter and passes through the pipeline and is connected with useless packagine machine admittedly, the solid of liquid commentaries on classics solid evaporimeter is discharged useless solid packagine machine carries out useless processing admittedly.
The invention is further configured to: the tail gas absorption treatment unit comprises a tail gas absorption tower and a tail gas washing pump, the tail gas emission of the liquid-to-solid evaporator is connected with the tail gas absorption tower through a pipeline, and absorption liquid discharged from the bottom of the tail gas absorption tower is connected with the tail gas washing pump through a pipeline; the tail gas washing pump is connected with the diffusion and dialysis membrane separator through a pipeline, and absorption liquid is used as water supplement of the diffusion and dialysis membrane for utilization.
The invention is further configured to: the method specifically comprises the following steps:
(1) pumping the collection tank containing the radioactive acidic wastewater into a resin adsorption column through a pump, and performing resin adsorption treatment on the wastewater;
(2) the resin column adopts two parallel absorption and desorption processes for adsorption treatment;
(3) the prepared resin material is loaded into a resin tree by using an automatic resin loading and unloading device, the waste liquid is quantitatively conveyed into the resin tree by using a metering pump after the resin material is sealed, and the adsorption tail liquid passes through a membrane separation device to generate recovered acid and separation residual liquid;
(4) concentrating the recovered acid by membrane separation to increase the concentration, and returning to the system for reuse;
(5) transferring the membrane separation residual liquid to an alkali reaction precipitation evaporation crystallization unit, using sodium hydroxide as a precipitator, and completing the operations of alkali precipitation, filtration, evaporation crystallization and the like in a precipitation evaporation crystallization reactor;
(6) the precipitate and the crystal generated by the basic reaction are used as solid waste for packaging treatment;
(7) tail gas generated by the alkali reaction precipitation evaporation crystallization unit is treated by a tail gas absorption treatment unit and then is discharged after reaching standards;
(8) the condensate of the acid concentration is reused as the raw material of the acid concentration evaporation unit.
The invention has the beneficial effects that:
the invention provides a device and a method for treating wastewater containing heavy metal and radioactive uranium elements, which can completely remove and separate acidic water containing radiation protection, salt and heavy metal, meet the requirements of safety and environmental protection, and have high removal efficiency of recycled resources and the radioactive uranium elements; the safety of personnel is ensured by realizing full automation of the resin adsorption automatic charging and discharging processes; the nitric acid is concentrated, evaporated, recycled and reused, so that resources are saved; the liquid-solid packaging is carried out by carrying out alkali reaction on heavy metals, precipitating, evaporating and crystallizing salt, so that unified treatment by workers is facilitated; the tail gas after evaporation and crystallization is absorbed and then discharged, so that the tail gas discharge requirement is ensured.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a schematic structural diagram of a preferred embodiment of the apparatus and method for treating wastewater containing heavy metals and radioactive uranium elements according to the present invention.
In the figure: 1. a radioactive-containing wastewater tank; 2. a resin adsorption column; 2A, a first adsorption column; 2B, a second adsorption column; 3. a cartridge filter; 4. a diffusion and dialysis membrane separator; 5. an evaporation concentration tower; 6. a condenser; 7. a condensate tank; 8. a lye tank; 9. a heavy metal collection tank; 10. a base reactor; 11. a filter; 12. a liquid-to-solid evaporator; 13. a solid waste packaging machine; 14. a tail gas absorption tower; 15. a wastewater feed pump; 16. an alkali liquor feed pump; 17. a heavy metal raffinate feed pump; 18. an acid recovery pump; 19. a condensate recovery pump; 20. and a tail gas washing pump.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
As shown in fig. 1, the device and method for treating wastewater containing heavy metals and radioactive uranium elements according to the present invention includes a resin adsorption unit, an diffusion and permeation membrane separation unit, an acid concentration and evaporation unit, a basic reaction precipitation and evaporation crystallization unit, a tail gas absorption and treatment unit, and mainly includes the following steps: 1) pumping wastewater containing acid, salt, heavy metal and radioactive uranium element into the resin adsorption unit through a pump for adsorption treatment, and pumping radioactive wastewater desorbed by resin into a calcination treatment process through a pump; 2) discharging the clear liquid adsorbed by the resin to the dialysis membrane separation unit, and separating acid water and heavy metals; 3) clean acid is discharged to the acid concentration evaporation unit for concentration process treatment after the diffusion chromatography membrane separation; 4) heavy metal residual liquid separated by the diffusion and permeation separation membrane enters the basic reaction precipitation evaporation crystallization unit for treatment; 5) carrying out solid waste treatment on the precipitated salt through evaporative crystallization packaging; 6) condensing and recovering water evaporated by acid concentration to be used as membrane separation pure water for supplementing water; 7) and the tail gas after the evaporation crystallization is washed and demisted by the tail gas absorption unit for emission.
Further, the features of the utility meter line include: 1) the pipelines, valves and other accessories in contact with the liquid in the reactor are made of corrosion-resistant materials; 2) all parts are required to be fully welded, and flaw detection treatment is carried out on the welding parts; 3) and the surface of the equipment (such as a tank body, an auxiliary system and the like) is required to be polished (surface roughness after polishing: and (3) outside: ra2.4, inner ra0.8); 4) the pressure transmitter, the thermocouple, the digital display meter, the motor, the instrument and the like related to the equipment are made of corrosion-resistant materials; 5) remote control is adopted, and the interlocking alarm function is that the equipment performs the related interlocking alarm function in the process.
Furthermore, all the devices of the process flows such as the resin adsorption unit, the diffusion dialysis membrane separation unit, the acid concentration evaporation unit, the basic reaction precipitation evaporation crystallization unit, the tail gas absorption treatment unit and the like are installed by adopting an integrated device, are intensively installed in a glove box, and are operated and overhauled through glove holes or in a long distance.
Further, the resin adsorption unit comprises a radioactive wastewater containing tank 1, a wastewater feed pump 15, a resin adsorption column 2 and a cartridge filter 113, the radioactive wastewater containing tank 1 is connected with the wastewater feed pump 15 through a pipeline, wastewater is pumped into the resin adsorption column 2, the resin adsorption column 2 comprises a first adsorption column 2A and a second adsorption column 2B, the first adsorption column 2A is used for adsorption, the second adsorption column 2B is used for resolution, the first adsorption column 2A is connected with the second adsorption column 2B in parallel, the resin adsorption column 2 is connected with the cartridge filter 113 through a pipeline, residual liquid of the resin adsorption column 2 is discharged to a calcination position for treatment, and clear liquid after adsorption is discharged to the cartridge filter 113 for secondary filtration.
Further, the dialysis membrane separation unit comprises a dialysis membrane separator 4, a heavy metal collection tank 9, a condensate recovery pump 19 and a tail gas washing pump 20, clear liquid filtered by the cartridge filter 113 enters the dialysis membrane separator 4, one side of the dialysis membrane separator 4 is connected with pure water through a pipeline, one part of the dialysis membrane separator 4 is connected with the condensate recovery pump 19 and the tail gas washing pump 20 through pipelines, and residual liquid discharged from the lower part of the dialysis membrane separator 4 is connected with the heavy metal collection tank 9 through a pipeline.
Further, the acid concentration and evaporation unit comprises an evaporation and concentration tower 5, a condenser 6, a condensate tank 7 and an acid recovery pump 18, clear liquid discharged by the dialysis membrane separator 4 is connected with the evaporation and concentration tower 5 through a pipeline, and the evaporation and concentration tower 5 is connected with the condenser 6 through a pipeline for evaporation and concentration by steam heating; the water condensed by the condenser 6 is connected with the condensed liquid tank 7 by a pipeline; and the acid concentrated by the evaporation concentration tower 5 is pumped into a recovery system through the acid recovery pump 18, and the water condensed by the condensate tank 7 is pumped into the dialysis membrane separator 4 through the condensate recovery pump 19 to be used as water supplement.
Further, the heavy metal collection tank 9 is connected with a heavy metal residual liquid feed pump 17 through a pipeline, a caustic solution tank 8 is arranged to be connected with an alkaline solution feed pump 16 through a pipeline, residual liquid of the heavy metal residual liquid feed pump 17 and alkaline solution of the alkaline solution feed pump 16 enter the alkaline reactor 10 together through a pipeline, precipitates reacted by the alkaline reactor 10 enter the filter 11 for filtration and precipitation, the precipitates filtered by the filter 11 enter the liquid-to-solid evaporator 12 for evaporation and crystallization, the liquid-to-solid evaporator 12 is connected with the solid waste packaging machine 13 through a pipeline, and solids of the liquid-to-solid evaporator 12 are discharged to the solid waste packaging machine 13 for solid waste treatment.
Further, the tail gas absorption treatment unit comprises a tail gas absorption tower 14 and a tail gas washing pump 20, the tail gas emission of the liquid-solid conversion evaporator 12 is connected with the tail gas absorption tower 14 through a pipeline, and the absorption liquid discharged from the bottom of the tail gas absorption tower 14 is connected with the tail gas washing pump 20 through a pipeline; the tail gas washing pump 20 is connected with the diffusion and dialysis membrane separator 4 through a pipeline, and absorption liquid is used as water supplement of the diffusion and dialysis membrane for utilization.
Further, the method specifically comprises the following steps:
(1) pumping the collection tank containing the radioactive acidic wastewater into a resin adsorption column 2 through a pump, and performing resin adsorption treatment on the wastewater;
(2) the resin column adopts two parallel absorption and desorption processes for adsorption treatment;
(3) the prepared resin material is loaded into a resin tree by using an automatic resin loading and unloading device, the waste liquid is quantitatively conveyed into the resin tree by using a metering pump after the resin material is sealed, and the adsorption tail liquid passes through a membrane separation device to generate recovered acid and separation residual liquid;
(4) concentrating the recovered acid by membrane separation to increase the concentration, and returning to the system for reuse;
(5) transferring the membrane separation residual liquid to an alkali reaction precipitation evaporation crystallization unit, using sodium hydroxide as a precipitator, and completing the operations of alkali precipitation, filtration, evaporation crystallization and the like in a precipitation evaporation crystallization reactor;
(6) the precipitate and the crystal generated by the basic reaction are used as solid waste for packaging treatment;
(7) tail gas generated by the alkali reaction precipitation evaporation crystallization unit is treated by a tail gas absorption treatment unit and then is discharged after reaching standards;
(8) the condensate of the acid concentration is reused as the raw material of the acid concentration evaporation unit.
The working principle of the device and the method for treating the wastewater containing the heavy metal and the radioactive uranium element is as follows:
according to the characteristics and treatment requirements of radioactive uranic wastewater in nuclear industry, the main impurities are as follows: fe. Impurity contents of Ni and Cr in trace uranium (uranium concentration: 1 mg/L): the total salt content is about 5g/L, wherein the contents of Ni and Fe are about more than 80%, and the anion is mainly NO 3-; concentration of free nitric acid: 3-4 mol/L; the dischargeable uranium content generated after wastewater treatment is less than 25 mug/L, the total salt content is less than 2g/L, the free water in solid waste is less than 1%, and nitric acid is separated and reused; firstly, uranium element containing radiation protection is treated, resin adsorption process is adopted, analysis is carried out, adsorption cycle process, when the waste liquid needing to be treated is adsorbed, the waste liquid obtained through analysis is sent to a precipitation calcining post for treatment, the adsorbed clean acid water passes through a diffusion dialysis membrane separation system, separation of acid and heavy metal is carried out, clean acid is concentrated and concentrated through an evaporation system, waste water containing heavy metal ions is subjected to reaction precipitation through an alkali liquor reaction precipitator, precipitation filter matters are subjected to evaporation crystallization through filtering salt type liquid transfer fixing equipment and are discharged to a packing machine for bag packing, evaporated steam is introduced to a tail gas absorption treatment unit through a fan for absorption and condensation, noncondensable gas is discharged, and water condensate is recycled through water replenishing of acid separation.
Resin adsorption unit: this unit only sets up an automatic resin of dismantling, and resin adsorption column 2 sets up the size according to the flow size, and resin adsorption unit adopts two adsorption columns to connect in parallel, and absorption, an analysis, adoption autonomous system carry out the control mode, and the resin column adsorbs the back that finishes, analyzes, and the analytic waste liquid is sent to deposit and is calcined the post and handle, adopts the resin feeding and the automatic control of unloading.
(1) Pretreatment of acid-containing wastewater: the acid-containing wastewater contains a small amount of solid impurities and suspended matters, and the suspended matters and small-particle impurities are completely removed in a cartridge filter 3 through a 1131 mu microfiltration system, so that the feed liquid meets the quality technical requirement of entering a diffusion and elution membrane separator 4.
(2) The waste acid recovered by the diffusion dialysis membrane separation unit adopts a dialysis principle and takes concentration difference as driving force, the whole device is formed by combining a diffusion dialysis membrane, a liquid distribution plate, a reinforcing plate, a liquid flow plate frame and the like, and different numbers of structural units are formed by a certain number of membranes; wherein each unit is divided into a dialysis chamber (A) and a diffusion chamber (B) by an anion homogeneous membrane, and when waste acid liquid and receiving liquid (pure water) are respectively introduced into two sides of the anion homogeneous membrane, the concentration of free acid and salt thereof on the waste acid liquid side is far higher than that on the water side. Due to the concentration gradient, the free acid and its salts in the spent acid tend to permeate the B compartment, but the membrane is selectively permeable, not allowing every ion to pass through with equal opportunity. Firstly, the anion membrane skeleton is positively charged, and has the characteristic of attracting negatively charged hydrated ions and repelling positively charged hydrated ions in the solution, so under the action of concentration difference, anions on the waste acid side are attracted and smoothly permeate through the membrane pore channels to enter one side of water. Meanwhile, ions with positive charges can be carried in the solution according to the requirement of electric neutrality, and the hydration radius of H + is smaller, so that the charge is less; the hydrated ion radius of the metal salt is larger and the metal salt is expensive, so that H + can preferentially pass through the membrane, and the acid in the waste liquid can be separated.
(3) Acid concentration and evaporation unit: and pumping the clear liquid absorbed by the resin into an evaporation concentration tower 5 through a pump for evaporation concentration, introducing water vapor into a tail gas absorption treatment unit for absorption, and pumping concentrated acid into a recovery tank. And conveying the recovered acid to an acid concentration reactor for concentration, so that the acidity is increased from 3-4 mol/L to 7-8 mol/L, returning the concentrated acid to a unit for reuse, and conveying the salt solution to an alkali reaction precipitation evaporation crystallization unit.
(4) Alkali reaction precipitation evaporation crystallization unit: pumping the stock solution into a reactor by using a vacuum pump, pumping the stock solution into an alkali liquor tank 8 by using a pump, then carrying out precipitation reaction in the reactor, separating precipitates, putting the precipitates into liquid-solid conversion equipment for evaporation and crystallization to obtain solids, discharging the solids to a packaging machine, carrying out drying and cake pressing for packaging, and packaging the dried filter cake, wherein the free water content is less than 1 percent according to the salt content of 5 g/L.
(5) A tail gas absorption treatment unit: the tail gas of the tail gas purification device shared by the acid concentration evaporation unit and the alkali reaction precipitation evaporation crystallization unit is induced by a fan to an absorption packed tower, and the final tail gas of a demister, a condenser 6 and other devices is washed and discharged to an exhaust system before reabsorption. The resulting condensate is used as a feed solution for membrane separation equipment in an acid separation system, and the condensate is required to have a resistivity of more than 10 M.OMEGA..
The invention provides a device and a method for treating wastewater containing heavy metal and radioactive uranium elements, which specifically comprise the following steps:
(6) pumping the collection tank containing the radioactive acidic wastewater into a resin adsorption column 2 through a pump, and performing resin adsorption treatment on the wastewater;
(7) the resin column adopts two parallel absorption and desorption processes for adsorption treatment;
(8) the prepared resin material is loaded into a resin tree by using an automatic resin loading and unloading device, the waste liquid is quantitatively conveyed into the resin tree by using a metering pump after the resin material is sealed, and the adsorption tail liquid passes through a membrane separation device to generate recovered acid and separation residual liquid;
(9) concentrating the recovered acid by membrane separation to increase the concentration, and returning to the system for reuse;
(10) transferring the membrane separation residual liquid to an alkali reaction precipitation evaporation crystallization unit, using sodium hydroxide as a precipitator, and completing the operations of alkali precipitation, filtration, evaporation crystallization and the like in a precipitation evaporation crystallization reactor;
(11) the precipitate and the crystal generated by the basic reaction are used as solid waste for packaging treatment;
(12) tail gas generated by the alkali reaction precipitation evaporation crystallization unit is treated by a tail gas absorption treatment unit and then is discharged after reaching standards;
(13) the condensate of the acid concentration is reused as the raw material of the acid concentration evaporation unit.
Compared with the prior art, the device and the method for treating the wastewater containing the heavy metal and the radioactive uranium element have the following beneficial effects:
the invention provides a device and a method for treating wastewater containing heavy metal and radioactive uranium elements, which can thoroughly remove and separate acidic water containing radiation protection, salt and heavy metal, meet the requirements of safety and environmental protection, and have high removal efficiency of recycled resources and radiation protection uranium elements; the safety of personnel is ensured by realizing full automation of the resin adsorption automatic charging and discharging processes; the nitric acid is concentrated, evaporated, recycled and reused, so that resources are saved; the liquid-solid packaging is carried out by carrying out alkali reaction on heavy metals, precipitating, evaporating and crystallizing salt, so that unified treatment by workers is facilitated; the tail gas after evaporation and crystallization is absorbed and then discharged, so that the tail gas discharge requirement is ensured.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "fixed" are to be construed broadly, e.g., as meaning either fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the embodiments and descriptions given above are only illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A wastewater treatment device containing heavy metal and radioactive uranium elements is characterized by comprising a resin adsorption unit, an diffusion and permeation membrane separation unit, an acid concentration and evaporation unit, an alkaline reaction precipitation and evaporation crystallization unit and a tail gas absorption and treatment unit,
the resin adsorption unit comprises a radioactive wastewater-containing tank (1), a wastewater feed pump (15), a resin adsorption column (2) and a security filter (113), wherein the radioactive wastewater-containing tank (1) is connected with the wastewater feed pump (15) through a pipeline, wastewater is pumped into the resin adsorption column (2), the resin adsorption column (2) comprises a first adsorption column (2A) and a second adsorption column (2B), the first adsorption column (2A) is connected with the second adsorption column (2B) in parallel, the resin adsorption column (2) is connected with the security filter (113) through a pipeline, residual liquid of the resin adsorption column (2) is discharged to a calcination position for treatment, and clear liquid after adsorption is discharged to the security filter (113) for secondary filtration;
the dialysis membrane separation unit comprises a dialysis membrane separator (4), a heavy metal collection tank (9), a condensate recovery pump (19) and a tail gas washing pump (20), clear liquid filtered by the cartridge filter (113) enters the dialysis membrane separator (4), one side of the dialysis membrane separator (4) is connected with pure water through a pipeline, one part of the dialysis membrane separator is connected with the condensate recovery pump (19) and the tail gas washing pump (20) through pipelines, and residual liquid discharged from the lower part of the dialysis membrane separator (4) is connected with the heavy metal collection tank (9) through a pipeline; the acid concentration and evaporation unit comprises an evaporation and concentration tower (5), a condenser (6), a condensate tank (7) and an acid recovery pump (18), clear liquid discharged by the diffusion dialysis membrane separator (4) is connected with the evaporation and concentration tower (5) through a pipeline, and the evaporation and concentration tower (5) is connected with the condenser (6) through a pipeline for heating, evaporating and concentrating acid through steam; the water condensed by the condenser (6) is connected with the condensed liquid tank (7) by a pipeline; acid concentrated by the evaporation concentration tower (5) is pumped into a recovery system through the acid recovery pump (18), and water condensed by the condensate tank (7) is pumped into the dialysis membrane separator (4) through the condensate recovery pump (19) to be used as water supplement; the heavy metal collection tank (9) is connected with a heavy metal raffinate feeding pump (17) through a pipeline, a lye tank (8) is arranged to be connected with an alkali lye feeding pump (16) through a pipeline, raffinate of the heavy metal raffinate feeding pump (17) and alkali lye of the alkali lye feeding pump (16) enter an alkaline reactor (10) through pipelines, a precipitate reacted by the alkaline reactor (10) enters a filter (11) for filtering and precipitating, a precipitate filtered by the filter (11) enters a liquid-solid transferring evaporator (12) for evaporating and crystallizing salt, the liquid-solid transferring evaporator (12) is connected with a solid waste packaging machine (13) through a pipeline, and solid of the liquid-solid transferring evaporator (12) is discharged to the solid waste packaging machine (13) for solid waste treatment; the tail gas absorption treatment unit comprises a tail gas absorption tower (14) and a tail gas washing pump (20), the tail gas emission of the liquid-solid conversion evaporator (12) is connected with the tail gas absorption tower (14) through a pipeline, and absorption liquid discharged from the bottom of the tail gas absorption tower (14) is connected with the tail gas washing pump (20) through a pipeline; the tail gas washing pump (20) is connected with the dialysis membrane separator (4) through a pipeline, and absorption liquid is used as water supplement of the dialysis membrane for utilization;
the method mainly comprises the following processing steps: (1) pumping a collection tank containing radioactive acidic wastewater into a resin adsorption column (2) through a pump, and performing resin adsorption treatment on the wastewater; (2) carrying out adsorption treatment on the resin column by adopting two parallel absorption and desorption processes; (3) filling the prepared resin material into a resin tree by using an automatic resin loading and unloading device, quantitatively conveying the waste liquid into the resin tree by using a metering pump after sealing, and producing recovered acid and separated residual liquid after the adsorption tail liquid passes through a membrane separation device; (4) concentrating the recovered acid by membrane separation to improve the concentration, and returning to the system for reuse; (5) transferring the membrane separation residual liquid to an alkali reaction precipitation evaporation crystallization unit, and using sodium hydroxide as a precipitator to finish alkali precipitation, filtration and evaporation crystallization operations in a precipitation evaporation crystallization reactor; (6) the precipitate and the crystal generated by the basic reaction are packaged and treated as solid waste; (7) tail gas generated by the alkali reaction precipitation evaporation crystallization unit is treated by a tail gas absorption treatment unit and then is discharged after reaching the standard; and (8) reusing the condensate of the acid concentration as a raw material of the acid concentration evaporation unit.
2. The apparatus for treating wastewater containing heavy metals and radioactive uranium elements according to claim 1, wherein: the features of the utility meter line include: 1) the pipelines, valves and other accessories in contact with the liquid in the reactor are made of corrosion-resistant materials; 2) all parts are required to be fully welded, and flaw detection treatment is carried out on the welding parts; 3) the surface of the equipment is required to be polished; 4) the instruments related to the equipment are made of corrosion-resistant materials; 5) remote control is adopted, and the interlocking alarm function is that the equipment performs the related interlocking alarm function in the process.
3. The apparatus for treating wastewater containing heavy metals and radioactive uranium elements according to claim 1, wherein: and all the equipment of the process flows of the resin adsorption unit, the diffusion dialysis membrane separation unit, the acid concentration evaporation unit, the basic reaction precipitation evaporation crystallization unit and the tail gas absorption treatment unit are installed by adopting an integrated device, are intensively installed in a glove box, and are operated and overhauled through a glove hole or in a remote distance.
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